Cellular material

ABSTRACT

The invention comprises the production of a cellular material by vulcanizing a mixture containing between 10% and 90% of an ebonite-forming rubber and sufficient vulcanizing agents to form an ebonite with the rubber, not more than 10% of a solid filler preferably in the absence of such filler, and a chemical blowing agent, whereby an ebonite structure is formed, so that, during the vulcanization, the chemical blowing agent decomposes or reacts to produce a gas, the viscosity of the composition during the production of the gas increasing whereby cells are retained in the composition wherein the mixture further contains between 5% and 87% of a bituminous material.

This is a continuation of application Ser. No. 345,575, filed Mar. 28,1973, now abandoned.

This invention relates to a cellular material. In particular it relatesto cellular materials containing bituminous substances.

It has previously been proposed to produce cellular materials containingbituminous materials. Such cellular materials have been formed by thereaction of a substance having at least two isocyanate groups, whichsubstances are hereinafter known as polyisocyanates, and the bituminousmaterial and the concurrent or subsequent foaming of the reacted produceto form a cellular material. The blowing or foaming agent is often thecarbon dioxide formed by the reaction of water with the polyisocyanate,or the reaction of the polyisocyanate with the bituminous material.

It has also been proposed to form cellular materials by the admixture ofan aqueous dispersion of a bituminous material and an aqueous dispersionof a rubber, foaming the mixture, and curing the cellular structure soformed. This prior proposed process results in the formation of flexibleopen celled cellular materials. The open cells are formed at leastduring the heating required for curing the rubber.

The present invention enables rigid cellular materials to bemanufactured containing bituminous materials and having a substantiallyclosed cell structure. The cellular materials are relatively strong butthe bituminous material enables a relatively low cost product to bemade.

Accordingly the invention provides a process for the production of acellular material by vulcanising a composition containing between 5% and87%, preferably at least 20% and less than 70%, of a bituminousmaterial, and between 10% and 90% of an ebonite-forming rubber, andpreferably at least 15% and less than 50% of the rubber, and sufficientvulcanising agents to form an ebonite with the rubber, not more than 10%of a solid filler, and a chemical blowing agent, whereby an ebonitestructure is formed, wherein, during the vulcanisation, the chemicalblowing agent decomposes or reacts to produce a gas, the viscosity ofthe composition during the production of the gas increasing wherebyclosed cells are retained in the composition.

The invention includes a foamable plastics composition containingbetween 5% and 87%, preferably at least 20% and less than 70%, of abituminous material, and between 10% and 90% of an ebonite-formingrubber, and preferably at least 15% and less than 50% of the rubber, andsufficient vulcanising agents to form an ebonite with the rubber, notmore than 10% of a solid filler, and a chemical blowing agent.

The invention further includes a cellular plastics material containingbetween 5% and 87%, preferably at least 20% and less than 70%, of abituminous material, and between 10% and 90% of an ebonite matrix, andpreferably at least 15% and less than 50% of the ebonite matrix, and notmore than 10% of a solid filler and including at least 25% by volume andpreferably at least 60% by volume, of closed cells.

Any bituminous material may, in principle, be employed in the presentinvention. The term "bituminous material" is a very wide generic termused for substances having relatively few chemical properties in common.Bituminous materials include the heavy ends from the fractionation ofpetroleum products, which are known in England as "bitumen" and inAmerica as "asphalt", such materials being hereafter referred to as"bitumen". It will be understood, however, that there may becompatibility problems between bitumen and the rubber employed, at leastin certain proportions. It is often preferred to employ, as thebituminous material, materials derived from coal. These materialsinclude coal tar and coal tar pitches, both of which are volatilematerials formed during the destructive distillation of coal, either inthe formation of coke or in the formation of combustile gases.

A particularly suitable bituminous material is coal digest which is theproduct formed by the treatment of coal with a pitch, tar, high-boilingoil or other solvent at an elevated temperature, for example 300° C to450° C, whereby the coal, or as much thereof as is practical todissolve, is dissolved in the pitch, tar, oil or other solvents. Thecoal is not present as s discrete phase, as is the case when the coal issuspended in the pitch, tar, oil or other solvent but is present insolution either as itself or in a solvolysed form.

It has been suggested that a coal digest may comprise a two phase systemincluding the pitch, tar, oil, or other solvent in which partiallysolvolysed coal is suspended. Insofar as the present invention isconcerned, such a suspension is a permanent one and the coal digest maybe considered as a single phase system. It is believed that the coaldigest may be partly colloidal.

There will be a certain proportion of the coal, mostly ash, which willbe insoluble in the pitch, tar, oil or other solvent. This proportionmay be filtered off. The coal digest may be considered as a solution orextract of coal. It may be unnecessary to filter off the insolublematter for purposes of the present invention as the insoluble matter,which will be finely divided, may be considered as a filler. It may beundesirable to employ a coal digest from a high-ash coal unfiltered.

The properties of the coal digest may be varied by varying the coal, thepitch, tar, oil or other solvent employed, the relative quantitiesthereof and other conditions, particularly temperature, of itsformation.

It may be convenient, particularly if a flexible or low density cellularmaterial is to be produced, to employ an oil-extended coal digest havinga needle penetration index, converted to a Ring and Ball softening pointof 85° C, of at least 10, and preferably at least 15.

A relatively high needle penetration index of the coal digest may oftenbe preferred in principle. However, it has been found that coal digesthaving needle penetration indices of above 25, converted to a softeningpoint of 85° C, are difficult to manufacture. A needle penetration indexof up to about 45, converted to a softening point of 85° C, would beparticularly suitable.

The coal digest may be extended with an oil or tar compatible with thecoal digest and such digest is known herein as an oil-extended coaldigest. For a coal digest having a softening point of about 85° C, itmay be convenient to add between 0.25 and 1 parts preferably between0.25 and 0.50 parts of oil or tar to each part of the coal digest.

The coal digest, when extended with the oil or tars, will generally havea density at 25° C of between 1 175 and 1 190 kg/m³, and the densityshould preferably be between 1 180 and 1 185 kg/m³.

The needle penetration index of a material is that distance that astandard needle penetrates vertically into a sample of the materialunder fixed conditions of loading, time and temperature. The method usedherein is that of Institute of Petroleum Standard method of testing IP49/67, which is believed not significantly to differ from the A.S.T.M.D5 method. In this method the needle penetration index is that distance,measured in tenths of a millimeter, that the standard needle penetratesinto the samples when applied thereto for 5 seconds by means of apenetrometer under a load of 100g and 25° C.

Any extension of the coal digest with oil or tar will involve thevariation of both the softening point and the needle penetration indexof the coal digest. Accordingly, the needle penetration index specifiedfor the purposes of this invention must be taken with reference to aparticular softening point of coal digest, 85° C. In respect of coaldigests having softening points other than 85° C the softening pointmust be converted to 85° C before the needle penetration index ismeasured. If the softening point of the coal digest is below 85° C, thecoal digest is distilled in an inert atmosphere or in vacuo to removelow boiling impurities. If the softening point of the coal digest isabove 85° C, oil or tar extender is added to diminish the softeningpoint to 85° C. In each case the distallation or addition is continueduntil the softening point is 85° C. The value of the needle penetrationindex of this product, having the 85° C softening point, is the needlepenetration index, converted to a softening point of 85° C, of theoriginal coal digest. Any extender employed should desirably be that, ifany, to be employed to extend the coal digest for use in the presentinvention. If no extender is to be employed to extend the coal digest,the oil or tar extender should have an immeasurably large needlepenetration index (over 500) under the standard conditions so that itdoes not contribute substantially to the converted needle penetrationindex of the coal digest.

The needle penetration index may be measured with the coal digestcontaining such portions of matter as is contained in the coal as isinsoluble therein and which, as is described, may be considered as afiller. However, the needle penetration index should not be measured inthe presence of additional filler.

The bituminous material may, in general, be extended with a fluxing oilor the like. Such oils are known in general, in relation to particularbituminous materials for which they are suitable. Such extendedmaterials will have a lower softening point than the unextendedbituminous materials. These may give to the composition to be foamed asoftening point undesirably lowered. In each case the amount of fluxingoil to be employed will be a matter for those of skill in the art offormulations. For bitumens, typical fluxing oils are naphthenichydrocarbon fractions. For materials of coal origin, typical fluxingoils are aromatic hydrocarbon fractions.

Any ebonite-forming natural or synthetic rubber may be employed,provided that it is sufficiently compatible with the bituminousmaterial. The degree of compatibility required will depend upon theparticular circumstances and is a matter for simple experiment.

The synthetic rubbers that form ebonites are, in general, those formedby the polymerization of conjugated dienes. The formation of the ebonitematrix is by the cross-linking of the unsaturated groups in the polymerchain with a vulcanising agent, usually sulphur, so that as many aspossible of such unsaturated groups are cross-linked. The typicalsynthetic rubbers that form ebonites are polymers, including copolymers,of butadiene and its homologues. Preferred copolymers of butadiene arewith acrylonitrile and/or styrene. Other rubbers of this type areisoprene rubbers and chloroprene rubbers (polychlorobutadiene). However,as chloroprene rubber is noted for its flexibility, the ebonite formedtherefrom is relatively flexible and its use is not preferred. Naturalrubber is a polyisoprene and forms an ebonite.

The normal vulcanising agent to be employed in the manufacture ofebonite is sulphur. Ebonite is characterised in that the vulcanisationof the rubber is carried out so that as many as possible of theunsaturated groups contained in the unvulcanised rubber arecross-linked, and so that the ebonite product becomes rigid andinextensible. The amount of vulcanising agent required for this varieswith the rubber but is generally at least 25 parts by weight per hundredparts of the rubber (p.h.r). of sulphur. In general, less than 50 p.h.r.will be used.

Accelerators and other additives will normally be employed in therubber, in general accord with ebonite or vulcanised rubbermanufacturing practice. Typical accelerators includeN,N'-diphenylthiourea N,N'-di-o-tolyl-guanidine,2-mercaptobenzthoiazole, tetramethylthiuram disulphide,tetramethylthiuram sulphide, zinc diethyldithiocarbonate, zinc2-mercaptobenzthiazole, zinc ethylphenyldithiocarbonate, zinciso-propylxanthate and sodium iso-propylxanthate. Typical anti-oxidantsand anti-ozonants that may be employed include N-phenylnaphthylamines,di-t-butyl-p-cresol, and N,N'-diphenyl-p-phenylenediamine.

By "chemical blowing agent" is meant those blowing agents which comprisecompounds or mixtures which react or decompose to produce a gas whichforms the cells in the cellular material. This does not include thosevolatile low molecular weight substances which are liquid at ambienttemperature but which are gases at the temperature at which the eboniteis formed. Chemical blowing agents include sodium bicarbonate andammonium bicarbonate, if appropriate in the presence of an organic acid,and azo compounds which decompose to give nitrogen on heating, forexample 2,2'azodiisobutyronitrile, benzenedisulphonhydrazide,di(4-benzenesulphonhydrazide)ether and azodicarbonamide.

The amount of blowing agent employed will depend on the desired densityof the cellular material. Cellular materials including over 60% or 80%by volume of cells may often be made.

Surface active agents, for example silicones, may be employed to promotea uniform fine cell structure. Other additives may also be used. In eachcase, careful regard must be had to the desired properties.

It may often be convenient to employ fire retardant substances in thecellular plastics material. Fire retardant substances that may beemployed are, in general, those that are used in the art of the rubberemployed. Examples of such fire retardant substances include brominatedorganic compounds and antimony trioxide, the latter generally inconjunction with a further fire retardant substance, for example amoniumfluoroborate, dichlorane and chlorinated waxes.

In some cases it may be desired to employ a particulate filler, in orderto improve the impact resistance or other properties of the cellularplastics composition or in order to diminish the cost thereof. However,the presence of a particulate filler in the cellular plasticscomposition may mean a deterioration in certain properties, for exampleabrasion resistance and cell structure, the latter particularly becausethe size of the filler will often be significant in comparison with thesize of the cell walls. It is therefore desirable that only smallquantities of filler, preferably less than 5%, should be employed.

The filler should preferably be finely divided, but it will beunderstood that, for various purposes, the particle size of the fillermay be varied. It is not necessary to have a purely particulate filler,and the filler may include shredded natural or synthetic organic orinorganic fibres. If fibres or large particles are present it may bemore difficult to foam the plastics composition evenly. Other suitablefillers include clays, including china clay and lanolin, shales, calciumcarbonate, fly ash, silica, carbon black and sawdust.

The foamable plastics composition is thoroughly mixed so that any solidsare dispersed therein, and the bituminous material and the rubber aremutually dispersed. It is generally unsatisfactory to employ emulsionsof the rubber and of the bituminous material, as the water will need tobe removed and the foamable plastics composition reworked before thecomposition is formed. This is, at least in part, because of therelatively high temperatures required for ebonite formation. Thefoamable plastics composition may advantageously be callendered toproduce a sheet.

The foamable plastics composition is after such mixing heated so thatthe rubber is partially vulcanised. The partial vulcanisation isadvantageously carried out at such a temperature that the chemicalblowing agent does not substantially decompose or react to produce gas,and to such an extent that the viscosity of the foamable plasticscomposition at the blowing temperature increases, with increasing amountof cure. The partially vulcanised mixture, or the foamable plasticscomposition, is heated to the blowing temperature, which is above thetemperature at which the blowing agent decomposes or reacts to producegas. The blowing agent decomposes while the rubber is vulcanised. Thevulcanisation of the rubber increases its strength so that the cells areretained therein. In order to produce closed cells it is generallynecessary to ensure that the viscosity and the strength of the mixtureis sufficiently high that the cell walls do not rupture once the cellshave been formed.

After the cells have been formed the vulcanisation is continued, ifdesired at an increased temperature, until an ebonite matrix is formed.The cells and cell walls will not normally substantially alter in shapeand size between the initial partial vulcanisation when the cells havebeen formed. The extent of the formation of the ebonite is a matter ofchoice having regard to the economics of production of the cellularmaterial. It is known in general to be difficult to manufacture acompletely cross-linked ebonite structure, and it is not normallynecessary completely to cross-link the rubber.

The exact heating procedure and the time of heating will depend on thechemical blowing agent, and the composition of the foamable plasticscomposition. It is not possible to indicate any method of choosing achemical blowing agent in conjunction with any particular heatingprocedure. This will be a matter of experiment, and it is normalpractice for one of ordinary skill in the art of cellular materialmanufacture, and in particular of cellular rubber manufacture, toconduct such experiments and to select heating procedures and blowingagents in order to produce cellular materials of desired cell structureand density. The use of the term "cell structure" includes not only theproportion of cells that are closed but also the size and eveness of theindividual cells.

In the manufacture of the ebonite, it is generally necessary to employ avulcanising temperature of at least 120° C, and a temperature of atleast 150° C is usual. It is not normal to employ a vulcanisingtemperature in excess of 200° C.

During the ebonite formation, or after the cells have been formed,temperatures of between 160° C and 180° C are normal. The temperaturesmay advantageously gradually be raised during the cell formation, untilit reaches a temperature suitable for the dormation of the ebonite.

One advantageous method of forming a cellular material is to introducethe foamable plastics material, shaped as required, for example in theform of a callendered sheet, into the mould cavity of a closed mould,the mould then being heated to heat the foamable plastics material, ifnecessary partially to vulcanise the rubber, and to cause the blowingagent to decompose or react to form the cells. The foamable plasticsmaterial may advantageously be partially vulcanised before it isinserted into the mould cavity. Once the cells have been formed andstabilised, the cellular material can advantageously be removed from themould and thereafter the vulcanisation can be continued until theebonite is formed.

According to a modification of the foregoing invention there is provideda further process for the production of a cellular material whichcomprises foaming a composition containing between 5% and 90%,preferably at least 20% and less than 70% of a coal digest and between10% and 90%, of a thermosettable resin system other than an epoxy resin,compatible with the coal digest in the proportion employed andpreferably at least 15% and less than 50% of the thermosettable resinsystem, and less than 10% of a finely divided filler, and preferably inthe substantial absence of any added filler, and curing thethermosettable resin to retain cells in the cured composition.

A foamable composition for use in this method contains between 5% and90%, preferably at least 20% and less than 70% of coal digest, andbetween 10% and 90% of a thermosettable resin system other than anepoxide resin compatible with the coal digest in the proportionemployed, and preferably at least 15% and less than 50% of thethermosettable resin, and less than 10% of a finely divided filler, andpreferably in the substantial absence of any added filler, and a blowingagent.

A cellular plastics material that can be prepared by this methodcontains between 5% and 90%, preferably at least 20% and less than 70%,of coal digest, and between 10% and 90% of a thermoset resin other thanan epoxide resin compatible with the coal digest in the proportionemployed, and preferably at least 15% and less than 50% of the thermosetresin, and less than 10% of a finely divided filler, and preferably inthe substantial absence of any added filler, and includes at least 60%by volume, and preferably at least 80% by volume of cells.

The blowing agent that may be employed in this modification may be thechemical blowing agent hereinbefore described. However any suitableblowing agent may be employed in order to form the cells in the cellularplastics material, provided that the active substance does not dissolvein th coal digest with the result that no cells are formed. Volatile lowmolecular weight organic substances having, preferably, not more thanfour carbon atoms, may, in principle, be employed, but they areparticularly subject to the solubility criterion. Examples of suchsubstances include halogenated hydrocarbons, for example chlorinatdhydrocarbons, fluorinated hydrocarbons, and chlorofluorinatedhydrocarbons, as well as hydrocarbons, for example propane and butane.

The blowing agent may be a substance that reacts with the thermosettingsystem or be a component of the thermosetting system. For example, ifthe thermosetting system includes a polyisocyanate, the polyisocyanatereacts with water to form carbon dioxide and an amine, which carbondioxide forms the cells.

Alternatively, gases, for example air, carbon dioxide or nitrogen, canbe whipped, or otherwise entrained, into the plastics composition to befoamed.

The thermosettable system employed should be sufficiently compatiblewith the coal digest in order that the thermosettable system can bethoroughly mixed with the coal digest. The suitability can be determinedby simple experiment. Suitable thermosettable systems include aldehydicresins, including hydrocarbon-formaldehyde resins, for examplexylene-formaldehyde resins and naphthalene-formaldehyde resins,furano-formaldehyde resins, phenol-formaldehyde resins, furfural resins,amine resins, for example melamine-formaldehyde resins andurea-formaldehyde resins and alkyd resins, which are polyesters derivedfrom at least a portion of compounds having either more than twohydroxyl groups or more than two carboxylic and groups.

The preferred thermoset resin is a polyurethane, which is formed by thereaction of a polyisocyanate with a compound having at least twoalcololic hydroxyl groups or amino N-H groups hereinafter referred to asisocyanate-reactive groups. The polyisocyanates that are employed arethose used in the manufacture of polyurethane cellular materials. Theseare generally the aromatic polyisocyanates, and it is normal to employmixed polyisocyanates. Such mixed polyisocyanates generally comprisemixed diisocyanates with a relatively small proportion oftriisocyanates. Examples of diisocyanates that may be employed are thediisocyanatotoluenes, di(4-isocyanatophenyl)methane,1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene,diisocyanatonaphthalenes, 4,4'-diisocyanatodiphenyl,di(4-isocyanatophenyl)ether, and di(isocyanate-cyclohexyl) methane.Polyisocyanates having more than two isocyanate groups that may beemployed include 2,4,6-triisocyanatotoluene, and(2,4,4'-triisocyanato)-diphenyl ether. A particularly suitable group ofpolyisocyanates which are reported to impart fire resistant propertiesto the cellular materials are the isocyanurates, which are formed by thetrimerisation of isocyanate groups and have a ##STR1##2,4,6-tirimino-1,3,5-trioxane ring structure. Such isocyanurates areformed by the trimerisation of the diisocyanates referred to above.

The compounds that have at least two isocyanate-reactive groups may bemonomeric or polymeric. Particularly suitable polymers are polyesters,polyesteramides and polyethers. Polyesters may be of the kind formed bythe reaction of a compound having a plurality of hydroxyl groups or theester forming derivatives thereof with a compound having a plurality ofcarboxylic acid groups or the ester forming derivatives thereof. Suchcompounds include ethylene glycol, diethylene glycol, glycerol,trimethylol propane, pentaerythritol, adipic acid, phthalic acids,trimellitic acid and pyromellitic acid. Polyethers may be derived, forexample, from ethylene oxide or propylene oxide by reaction with acompound having a plurality of hydroxyl groups. Polyesteramides areanalogous to polyesters, but employing a proportion of amines, in placeof the alcohols, for example ethanolamine. There may also be presentother compounds used in the manufacture of polyurethane cellularmaterials, for example basic compounds which may act as catalysts,including potassium acetate, triethylamine, triethylene diamine andN-alkylpyrrolidines.

Any suitable conventional technique of foaming or blowing and settingthe resin may be employed to form the cellular plastics materialaccording to this modification of the invention. The foamable plasticscomposition may be introduced into a closed mould which is then heatedso that the blowing agent produces cells and expands the foamableplastics composition to fill the mould while concurrently curing theresin. The cellular plastic material may also be formed by thefree-blown process, in which the components of the foamable compositionare mixed and, if appropriate, heated, and the foamable compositionfoams and cures.

According to a further modification of the invention, in the manufactureof the cellular material having the ebonite structure and the foamablecomposition therefor, in conjunction with the coal digest having apenetration, converted to a Ring and Ball softening point of 85° C, ofat least 10, in excess of 10% and less than 40% of the finely dividedparticulate filler may be employed.

The following non-limitative examples illustrate the invention.

EXAMPLE 1

For each of the following formulations the constituents are milledtogether on a two-roll mill and then moulded. The moulded product isheated in a closed mould to 170° C for 30 minutes at which temperaturethe blowing agent decomposes and the rubber vulcanises. A cellularplastics material having the density indicated below is formed.Formulations 1 to 3 are rigid materials.

    ______________________________________                                        Formulation            1      2      3                                        ______________________________________                                        Coal tar pitch softening point 110° C                                                         69                                                     Coal tar pitch softening point  80° C                                                                55     77.3                                     Styrene-butadiene rubber                                                                             20            15                                       Natural rubber                30                                              Sulphur                7      10     5                                        Azo blowing agent      1      1      1                                        Zinc oxide             1      1.5    0.7                                      Calcium oxide          0.5    --     --                                       Stearic acid           1      1.5    0.7                                      Di(benzothiazol-2-yl)disulphide                                                                      0.5    1      0.3                                      Density of product kg/m.sup.3                                                                        220    260    400                                      ______________________________________                                    

EXAMPLE 2

For each of the following formulations, the constituents are blendedtogether using internal mixers and two roll mills at below 100° C. Thefoamable compositions are sheeted on a calender and placed in a mouldcavity. The mould is then heated for the time indicated and at thetemperature indicated. The blowing agent decomposes to form cells and anebonite is formed. The products have closed cells with low waterabsorption and thermal conductivity as shown from the following table,the properties being determined by British Standard methods.

    __________________________________________________________________________    Type of Rubber      S.B.R. Natural                                                                            Nitrile                                                                            Polybutadiene                            __________________________________________________________________________    Rubber, %            20     15  20   22                                       Sulphur, %          6      5    6    5                                        Zinc oxide, %       2      2    2.5  2                                        Stearic acid, %     0.8    0.4  0.6  0.5                                      Dibenzthiazyl disulphide, %                                                                       1.5    --   1.8  1.5                                      Mercaptobenzthiazole, %                                                                           --     0.4  --   --                                       Benzene sulphonhydrazide, %                                                                       3.0    2.0  --   3.5                                      Di(4-benzenesulphonhydrazide)ether                                                                --     --   3.0  --                                       Pitch (115-120° C R & B), %                                                                balance                                                                              --   balance                                                                            balance                                  Coal digest (80° C R & B), %                                                               --     balance                                                                            --   --                                       Cure temperature, ° C                                                                      170    150  170  160                                      Cure period, min.    30     50   40   30                                      Density (Kg/m.sup.3)                                                                              240    300  250  400                                      Water absorption, % v/v after                                                 1 week total immersion                                                                            0.55   0.50  0.62                                                                              0.48                                     Water vapour transmission                                                     (g/m.sup.2 s bar)    0.5×10-3                                                                      --   --   --                                       Linear coefficient of                                                         Thermal expansion,                                                            20° C, (per ° C)                                                                    10.3×10-5                                                                      --   --   --                                       Thermal conductivity, at 20° C                                         (Wm/m.sup.2 ° C)                                                                           0.043  0.050                                                                              0.045                                                                              0.068                                    Tensile strength at 20° C kN/m.sup.2                                                       672    --   --   --                                       Flexural strength at 20° C kN/m.sup.2                                                      1197   1300 1050 5020                                     Compression strength at 20° C kN/m.sup.2                                                   980    1000 980  4200                                     Impact strength at 20° C (g)                                                                0.03  --   --   --                                       __________________________________________________________________________     SBR is a copolymer rubber of styrene and butadiene                       

EXAMPLE 3

For the following formulations an oil-extended coal digest wasmanufactured by digesting coal with a coal tar pitch at 300° C atatmospheric pressure, and was then extended with anthracene oil to givea coal digest having a Ring and Ball softening point of 85° C and aneedle penetration index of 25.

The components of the formulations were milled together on a two-rollmill. After mixing, the formulations were moulded and heated to 170° Cat which temperature the blowing agent decomposed and the rubbervulcanised to form an ebonite rigid cellular materials having closedcells. and densities indicated below were formed.

    ______________________________________                                        Formulation          4         5                                              ______________________________________                                        Styrene-butadiene rubber                                                                           20        10                                             Zinc oxide           2         1                                              Stearic acid         2         1                                              Di(benzothiazol-2-yl)disulphide                                                                    1         0.5                                            Calcium oxide        0.5       0.25                                           Coal digest          66.5      83.25                                          Sulphur              7         3                                              Di(4-benzenesulphonhydrazide)ether                                                                 1         1                                              Density of cellular product kg/m.sup.3                                                             320       500                                            ______________________________________                                    

A mixture is formed from the following at slightly above ambienttemperature:

    ______________________________________                                        Coal digest (as Example 3)                                                                           70                                                     Bis(4-isocyanatophenyl)methane                                                                       70                                                     Strained anthracene oil                                                                              25                                                     ______________________________________                                    

The following are then added to the mixture and thoroughly mixed in:

    ______________________________________                                        Stannous octanoate    0.5                                                     Silicone surfactant   0.5                                                     ______________________________________                                    

Finally, 8 parts of water are mixed in and the mixture is poured into amould. The water reacts with the isocyanate groups forming carbondioxide. A semi-rigid non-friable cellular plastics material having adensity of 80 kg/m³ is formed.

EXAMPLE 5

An isocyanurate formed by trimerising di(4-isocyanatophenyl) methane wasemployed in the manufacture of a cellular material, 60 parts of theisocyanurate, 20 parts of the coal digest (as Example 3) and 5 parts oftrichlorofluoramethane were mixed together. 15 parts of a mixture ofcompounds having at least two hydroxyl groups per molecule andadditionally containing catalysts and surfactants, which mixture iscommon to the art of polyurethane cellular materials, were mixed in withthe cellular material so that the isocyanurate reacts exothermicallywith the mixture of compounds having at least two hydroxyl groups. Thetrichlorofluoromethane volatilises and a rigid cellular material havinga density of 48 kg/m³, a thermal conductivity of 0.035 Wm/m² K and asubstantially closer cell structure is formed.

EXAMPLE 6

A coal digest was manufactured by digesting coal with pitch at 300° C atatmospheric pressure and subsequently extending the product withanthracene oil to give a coal digest having a Ring and Ball softeningpoint of 85° C and a needle penetration index of 25.

The following constituents were mixed on a two-roll mill:

    ______________________________________                                        Formulation          6         7                                              ______________________________________                                        Styrene-butadiene rubber                                                                           12        7                                              Sodium bicarbonate   4         4                                              Sulphur              4         2                                              Stearic acid         0.2       0.1                                            Di(benzothiazol-2-yl)disulphide                                                                    0.6       0.3                                            Zinc oxide           2         1                                              Coal digest          52.2      55.6                                           Finely divided fly ash                                                                             25        --                                             Finely divided clay  --        30                                             ______________________________________                                    

When thoroughly mixed, the mixtures were placed in closed moulds andheated to 175° C for thirty minutes during which time the sodiumbicarbonate decomposed and the rubber vulcanised to an ebonite. Rigidcellular materials having densities, in the case of formulation 6, 720kg/m³ and, in the case of formulation 7, 800 kg/m³ are formed.

All percentages in this specification and claims are by weight of thetotal composition unless the contrary intention is specified.

We claim:
 1. A process for the production of a cellular material byvulcanizing a mixture containing between 10% and 50% of a mixture ofrubber together with sufficient vulcanizing agents to form an ebonitewith the rubber, not more than 10% of a solid filler, and a chemicalblowing agent, whereby an ebonite structure is formed, so that, duringthe vulcanization, the chemical blowing agent decomposes or reacts toproduce a gas, the viscosity of the composition during the procedure ofthe gas increasing whereby cells are retained in the composition whereinthe mixture further contains between about 52% and 87% of a bituminousmaterial.
 2. The process claimed in claim 1 in which the mixture foamedcontains no added filler.
 3. The process claimed in claim 1 in which thebituminous material is coal digested in pitch, tar or tar oil.
 4. Theprocess claimed in claim 2 in which the rubber is selected from naturalrubber and synthetic rubbers, said synthetic rubber being a homopolymeror copolymer of butadiene or isoprene.
 5. The process claimed in claim 4in which the synthetic rubber is a copolymer of butadiene or isoprenewith acrylonitrile or styrene.
 6. The process claimed in claim 4 inwhich before being foamed the mixture is so mixed that any solids aredispersed and the bituminous material and the rubber are mutuallydispersed.
 7. A cellular plastics material containing between about 52%and 87% of a bituminous material, and between 10% and 50% of an ebonitematrix formed of rubber and a vulcanizing agent filler and including atleast 25% by volume of closed cells.
 8. The cellular plastics materialclaimed in claim 7 in which the bituminous material is coal digested inpitch, tar or tar oil.
 9. The cellular plastics material claimed inclaim 7 in which the ebonite matrix is derived from a natural rubber ora synthetic rubber, said synthetic rubber being a homopolymer orcopolymer of butadiene or isoprene.
 10. The cellular plastics materialclaimed in claim 9 including at least 60% by volume of cells.